EP0553210B1 - A polymerisation inhibitor system comprising air and a N-phenyl-1,4-benzoquinoneimine compound - Google Patents
A polymerisation inhibitor system comprising air and a N-phenyl-1,4-benzoquinoneimine compound Download PDFInfo
- Publication number
- EP0553210B1 EP0553210B1 EP91919065A EP91919065A EP0553210B1 EP 0553210 B1 EP0553210 B1 EP 0553210B1 EP 91919065 A EP91919065 A EP 91919065A EP 91919065 A EP91919065 A EP 91919065A EP 0553210 B1 EP0553210 B1 EP 0553210B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- hydrogen
- alkyl
- cycloalkyl
- alkaryl
- phenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- VDPQJTVDNZYPLU-UHFFFAOYSA-N CN(C)c1ccc(CN=C(C=C2)C=CC2=O)cc1 Chemical compound CN(C)c1ccc(CN=C(C=C2)C=CC2=O)cc1 VDPQJTVDNZYPLU-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
- C07C251/20—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups being part of rings other than six-membered aromatic rings
- C07C251/22—Quinone imines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/20—Use of additives, e.g. for stabilisation
Definitions
- This invention is directed to a polymerization inhibitor system for vinyl aromatic compounds comprising (a) air and an N-phenyl-1,4-benzoquinoneimine compound; and, optionally, (b) an aryl-substituted phenylenediamine compound.
- this invention is directed to a vinyl aromatic composition stabilized against polymerization by such polymerization inhibitor system, as well as to a method of stabilizing a vinyl aromatic composition against polymerization which method comprises adding an effective amount of such polymerization inhibitor system.
- vinyl aromatic compounds such as monomeric styrene, divinyl benzene and lower alkylated styrenes (such as alpha-methylstyrene and vinyltoluene) typically produce products contaminated with various impurities, such as benzene, toluene and the like. These impurities must be removed in order for the monomer product to be suitable for most applications.
- Such purification of vinyl aromatic compounds is generally accomplished by distillation.
- the compounds which are commercially employed as such polymerization inhibitors are of the dinitrophenolic class.
- Drake et al in U. S. Pat. 2,526,567, show the stabilization of nuclear chlorostyrenes employing 2,6-dinitrophenols.
- U. S. Pat. 4,105,506, to Watson discloses the use of 2,6-dinitro-p-cresol as a polymerization inhibitor for vinyl aromatic compounds.
- dinitrophenols are effective polymerization inhibitors, there are several disadvantages associated with their use, either alone or in blends.
- dinitrophenols are solids that, if subjected to temperatures above their melting points, are unstable and may explode (see U. S. Pat. 4,457,806).
- dinitrophenols are highly toxic, many having a dermal LD50 (rabbit) in ethylbenzene of less than 2 g/Kg.
- halogenated vinyl aromatic compounds such as bromostyrene
- an amine polymerization inhibitor selected from the group consisting of certain alkyl-substituted phenylenediamine compounds and phenothiazine compounds in the presence of air.
- US-A 4 692 544 discloses a polymerization inhibitor system wherein a compound of the formula R-X-Ar1-NH-Ar2-Y-H is used which shall be in reduced form. It is possible according to this document to use up to 20 percent of the total weight of the inhibitor in the oxidized form.
- this invention is directed to a vinyl aromatic polymerization inhibitor system comprising: air and an N-phenyl-1,4-benzoquinoneimine compound having the formula I wherein R is H; NR1R2 wherein R1 and R2 are independently selected from the group consisting of hydrogen, C1-C8 alkyl, C6-C10 aryl, C7-C16 alkaryl and C3-C8 cycloalkyl; or OR3 wherein R3 is hydrogen, C4-C8 cycloalkyl or C1-C8 alkyl; and R4 and R5 are independently selected from the group consisting of hydrogen, C1-C8 alkyl, C4-C8 cycloalkyl, C6-C10 aryl, and C7-C16 alkaryl.
- this invention is directed to a polymerization inhibitor system comprising:
- this invention is directed to a vinyl aromatic composition stabilized against polymerization, said composition comprising a vinyl aromatic compound together with air and a benzoquinoneimine compound of formula I and optionally, a phenylenediamine of formula II.
- N-phenyl-1,4-benzoquinoneimines of formula I which can be employed herein are those wherein R4 and R5 are hydrogen and R1 is C1-C8 alkyl.
- a more preferred benzoquinoneimine is where R4 and R5 are hydrogen and R1 and R2 are methyl, i.e.,
- the compound of formula III is commercially available for example, from the Aldrich Chemical Company, Milwaukee, WI and is known as phenol blue. Phenol blue is a known oxidation-reduction indicator, as is discussed in Oxidation-Reduction Potentials of Organic Systems , Williams and Watkins Press, 1960., by W.M. Clark.
- phenol blue has been used as a reactant in organic complexing reactions (Menger et al in J. Am. Chem. Soc. , 103(19) 5938 in 1981), and its use as an anti-tumor agent (Hodnett et al., J. Biol. Phys , 5(1-2), 24-48, 1977).
- indophenol Another preferred compound of this benzoquinoneimine class is indophenol, whose structure is Indophenol has long been used to synthesize sulfur dyes. More recently, indophenol has been used on an anti-tumor agent, (CHEM. ABSTRS. 107(7):51493y and 97(21):174475b) and as a deactivator in water-splitting systems of photosynthesis.
- phenylenediamine component of the inhibitory blends of this invention which is optionally present, is of the formula II above.
- Preferred compounds include those wherein the amine groups are in the para position.
- Particularly preferred compounds are the para-phenylenediamines wherein R7 and R8 are hydrogen; R6 is phenyl; and R9 is C3-C8 alkyl or C3-C8 cycloalkyl.
- phenylenediamine compounds which may be employed include N-phenyl-N'-isopropyl-p-phenylenediamine, N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine, N-phenyl-N'-(1,4-dimethylpentyl)-p-phenylenediamine and N-phenyl-N'-cyclohexyl-p-phenylenediamine. Moreover, mixtures of phenylenediamine compounds may also be employed.
- the phenylenediamine compounds may be of the oxygenated species as described in U.S. Pat. 4,774,374 to Abruscato et al.
- the presence of air may add to the efficacy of the inhibitors of the present invention.
- N-phenyl-1,4-benzoquinoneimines and blends therewith in ethylbenzene of this invention have dermal LD50 (rabbit) values of greater than 2 g/kg.
- the dermal LD50 (rabbit) in ethylbenzene values of dinitrophenol: phenylenediamine blends can be said to be "relatively non-toxic” but obviously the dinitrophenol component cannot be so labelled. Both components of the blends of this invention, however, can be labelled "relatively non-toxic".
- N-phenyl-1,4-benzoquinoneimines and the phenylenediamine compounds of this inventions are generally employed in weight ratios of between 10:1 and 1:10.
- weight ratios of between 4:1 and 1:4 are employed, with ratios of between 2:1 and 1:2 being particularly preferred.
- the polymerization inhibitor compositions of this invention may further comprise an aromatic hydrocarbon solvent.
- aromatic hydrocarbon solvent examples include benzene, toluene, xylene, ethylbenzene and other alkyl-benzenes as well as vinyl aromatic compounds themselves such as styrene and alpha-methylstyrene.
- solvents when solvents are employed the hydrogenated precursors of the vinyl aromatic to be stabilized are the preferred solvents.
- ethylbenzene is the preferred solvent.
- isopropylbenzene is the preferred solvent.
- the stabilized vinyl aromatic composition of this invention may be in the form of a reaction mixture additionally comprising the starting materials of the vinyl aromatic compound to be stabilized as well as by-products of the production process.
- the reaction mixture will typically include starting materials such as benzene, ethylbenzene and ethylene, as well as by-products such as diethylbenzene and vinyl toluene.
- the primary use of the polymerization inhibitor systems of this invention is to prevent the polymerization of vinyl aromatics during purification and/or distillation to remove unreacted starting materials and distillable by-products.
- this involves the sequential distillation of the vinyl aromatic reaction product through a plurality of distillation columns. In the first of such columns, a relatively large amount of starting material and by-products will be present, while in the last column essentially pure vinyl aromatic compound (plus polymerization inhibitors and heavy, nondistillable byproducts) will be present.
- the method of this invention involves adding to a vinyl aromatic compound an effective amount of the "instant polymerization inhibitor system."
- an effective amount of the "instant polymerization inhibitor system” When the polymerization inhibitor system of this invention is employed during the purification and/or distillation of vinyl aromatic compounds, it is preferred that oxygen, whether in the form of air or otherwise, be present. It is also noted that the polymerization inhibitor system of this invention will be effective for uses other than during distillation, e.g., during the shipment or storage of vinyl aromatic compounds.
- the methods of this invention comprise the addition to a vinyl aromatic composition of an effective amount of the instant polymerization inhibitor system.
- an effective amount refers to that amount of inhibitor which is needed to prevent the formation of more than about 1 weight percent of vinyl aromatic polymer in less than about 3 hours at temperatures of between 90°C and 150°C.
- the amount of polymerization inhibitor required will vary somewhat (based upon such factors as e.g. the particular vinyl aromatic compound stabilized; the particular benzoquinoneimine and phenylenediamine species employed;) such an effective amount may be readily determined by routine experimentation. In general, such an effective amount will be between 50 and 1,500 parts per million by weight of vinyl aromatic compound.
- the polymerization inhibitor system of this invention will provide stability against vinyl aromatic polymerization at temperatures typically employed for the purification of vinyl aromatic compounds (i.e., from 90° to 140°C) for periods well in excess of those typically employed for such purification. This stability is achieved without the use of undesirably toxic dinitrophenolic compounds which are generally employed in commercial operations today.
- styrene To a fifty milliliter flask charged with forty grams of styrene were added the various amounts and types of inhibitors as indicated in Tables 1 and 2 below.
- the inhibitors tested include phenol blue (PB), N-(1,4-Dimethyl)-N'-phenyl-p-phenylenediamine (I-3), and PB:I-3 blends.
- the flask was fitted with a magnetic stirrer and septum closure with a syringe needle as a vent and heated in an oil bath to 118°C (plus or minus 2°C).
- the flask was purged with approximately 5 cc/min of air (invention) or nitrogen (comparison) passed beneath the liquid surface during the period of the test.
- samples were removed from the flask periodically and tested for degree of polymerization by measuring the changes in refractive index. The time until onset of polymerization which is defined as the point at which one (1) weight percent of the styrene had polymerized, was determined in each example and tabulated below.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polymerisation Methods In General (AREA)
- Pyrrole Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US60005690A | 1990-10-18 | 1990-10-18 | |
US600056 | 1990-10-18 | ||
PCT/US1991/007188 WO1992006939A1 (en) | 1990-10-18 | 1991-09-30 | Benzoquinoneimines as vinyl aromatic polymerization inhibitors |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0553210A1 EP0553210A1 (en) | 1993-08-04 |
EP0553210B1 true EP0553210B1 (en) | 1995-07-19 |
Family
ID=24402181
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP91919065A Expired - Lifetime EP0553210B1 (en) | 1990-10-18 | 1991-09-30 | A polymerisation inhibitor system comprising air and a N-phenyl-1,4-benzoquinoneimine compound |
Country Status (12)
Country | Link |
---|---|
US (2) | US6039895A (ja) |
EP (1) | EP0553210B1 (ja) |
JP (1) | JPH05506248A (ja) |
KR (1) | KR100215505B1 (ja) |
AR (1) | AR247750A1 (ja) |
AU (1) | AU658376B2 (ja) |
BR (1) | BR9106956A (ja) |
CA (1) | CA2092534C (ja) |
DE (1) | DE69111462T2 (ja) |
ES (1) | ES2089240T3 (ja) |
MX (1) | MX9101669A (ja) |
WO (1) | WO1992006939A1 (ja) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0553210B1 (en) * | 1990-10-18 | 1995-07-19 | UNIROYAL CHEMICAL COMPANY, Inc. | A polymerisation inhibitor system comprising air and a N-phenyl-1,4-benzoquinoneimine compound |
US5648573A (en) * | 1995-06-12 | 1997-07-15 | Betzdearborn Inc. | Compositions and methods for inhibiting vinyl aromatic monomer polymerization |
EP1513789B1 (en) * | 2002-06-12 | 2013-04-03 | Stone & Webster Process Technology, Inc. | Eb/sm splitter heat recovery |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2526567A (en) * | 1948-07-06 | 1950-10-17 | Dow Chemical Co | Stabilization of nuclear chlorostyrenes by 2, 6-dinitrophenols |
US3004042A (en) * | 1958-09-15 | 1961-10-10 | Shell Oil Co | Free radicals of 4,4'-bis(2,6-di-tert-alkylhydroxyphenyl) amines |
LU67860A1 (ja) * | 1973-06-22 | 1975-03-27 | ||
US4105506A (en) * | 1977-02-24 | 1978-08-08 | Cosden Technology, Inc. | Polymerization inhibitor for vinyl aromatic compounds |
US4457806A (en) * | 1982-06-28 | 1984-07-03 | The Sherwin-Williams Company | Process for vinyl aromatic monomer polymerization inhibition |
US4633026A (en) * | 1983-02-22 | 1986-12-30 | Ethyl Corporation | Process for preparing ring-halogenated vinyl aromatic monomers |
CA1224811A (en) * | 1983-04-11 | 1987-07-28 | James R. Butler | Polymerization inhibition process for vinyl aromatic compounds |
US4466905A (en) * | 1983-04-11 | 1984-08-21 | Cosden Technology, Inc. | Polymerization inhibition process for vinyl aromatic compounds |
US4552697A (en) * | 1983-05-12 | 1985-11-12 | Miles Laboratories, Inc. | Compound useful in detecting ions and method of preparing it |
US4540520A (en) * | 1983-05-12 | 1985-09-10 | Miles Laboratories, Inc. | Compound useful in detecting ion and method of preparing it |
GB2159826A (en) * | 1984-06-04 | 1985-12-11 | Gen Electric | Stabilization of polyfunctional acrylate compositions against premature anaerobic polymerization |
US4692544A (en) * | 1985-08-23 | 1987-09-08 | Sandoz Ltd. | Inhibiting polymerization of ethylenically unsaturated monomers |
US4915873A (en) * | 1988-01-22 | 1990-04-10 | Uniroyal Chemical Company, Inc. | Polymerization inhibitor composition for vinyl aromatic compounds |
EP0553210B1 (en) * | 1990-10-18 | 1995-07-19 | UNIROYAL CHEMICAL COMPANY, Inc. | A polymerisation inhibitor system comprising air and a N-phenyl-1,4-benzoquinoneimine compound |
US5312952A (en) * | 1992-04-23 | 1994-05-17 | Uniroyal Chemical Company, Inc. | Polymerization inhibitor for vinyl aromatics |
US5470440A (en) * | 1994-04-19 | 1995-11-28 | Betz Laboratories, Inc. | Method for inhibiting vinyl aromatic monomer polymerization |
US5773676A (en) * | 1996-08-06 | 1998-06-30 | Phillips Petroleum Company | Process for producing olefins and aromatics from non-aromatics |
-
1991
- 1991-09-30 EP EP91919065A patent/EP0553210B1/en not_active Expired - Lifetime
- 1991-09-30 BR BR919106956A patent/BR9106956A/pt not_active Application Discontinuation
- 1991-09-30 JP JP91517301A patent/JPH05506248A/ja active Pending
- 1991-09-30 DE DE69111462T patent/DE69111462T2/de not_active Expired - Lifetime
- 1991-09-30 ES ES91919065T patent/ES2089240T3/es not_active Expired - Lifetime
- 1991-09-30 KR KR1019930701069A patent/KR100215505B1/ko not_active IP Right Cessation
- 1991-09-30 WO PCT/US1991/007188 patent/WO1992006939A1/en active IP Right Grant
- 1991-09-30 CA CA002092534A patent/CA2092534C/en not_active Expired - Lifetime
- 1991-09-30 AU AU88414/91A patent/AU658376B2/en not_active Ceased
- 1991-10-08 AR AR91320879A patent/AR247750A1/es active
- 1991-10-18 MX MX9101669A patent/MX9101669A/es unknown
-
1994
- 1994-07-18 US US08/276,685 patent/US6039895A/en not_active Expired - Lifetime
-
1999
- 1999-12-14 US US09/461,146 patent/US6222080B1/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
CA2092534A1 (en) | 1992-04-19 |
DE69111462T2 (de) | 1996-01-25 |
KR100215505B1 (ko) | 1999-08-16 |
US6222080B1 (en) | 2001-04-24 |
WO1992006939A1 (en) | 1992-04-30 |
AR247750A1 (es) | 1995-03-31 |
ES2089240T3 (es) | 1996-10-01 |
KR930702257A (ko) | 1993-09-08 |
AU8841491A (en) | 1992-05-20 |
CA2092534C (en) | 2003-01-07 |
BR9106956A (pt) | 1993-08-31 |
JPH05506248A (ja) | 1993-09-16 |
EP0553210A1 (en) | 1993-08-04 |
MX9101669A (es) | 1992-07-08 |
DE69111462D1 (de) | 1995-08-24 |
AU658376B2 (en) | 1995-04-13 |
US6039895A (en) | 2000-03-21 |
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